WO2000005236A1 - Catalyseur au cyclopentadienyl/phosphinime avec un et un seul ligand activable - Google Patents

Catalyseur au cyclopentadienyl/phosphinime avec un et un seul ligand activable Download PDF

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WO2000005236A1
WO2000005236A1 PCT/CA1999/000526 CA9900526W WO0005236A1 WO 2000005236 A1 WO2000005236 A1 WO 2000005236A1 CA 9900526 W CA9900526 W CA 9900526W WO 0005236 A1 WO0005236 A1 WO 0005236A1
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radical
reactor
mol
polymerization
olefin polymerization
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PCT/CA1999/000526
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English (en)
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Rupert Edward Von Haken Spence
Douglas W. Stephan
Stephen John Brown
Dusan Jeremic
Qinyan Wang
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Nova Chemicals (International) S.A.
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Priority to BRPI9912316-9A priority Critical patent/BR9912316B1/pt
Priority to AT99924614T priority patent/ATE228141T1/de
Priority to DE69904061T priority patent/DE69904061T2/de
Priority to EP99924614A priority patent/EP1112276B1/fr
Priority to AU41263/99A priority patent/AU4126399A/en
Priority to JP2000561192A priority patent/JP4377061B2/ja
Publication of WO2000005236A1 publication Critical patent/WO2000005236A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/535—Organo-phosphoranes
    • C07F9/5355—Phosphoranes containing the structure P=N-
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Definitions

  • This invention relates to an olefin polymerization catalyst component which is an organometallic complex having three ligands, namely a cyclopentadienyl ligand, a phosphinimine ligand and only one activatable ligand.
  • Certain "metallocenes” are highly productive catalysts for olefin polymerization when used in combination with an appropriate activator (see, for example, United States Patent (“USP”) 4,542,199 (Sinn et al) and USP 5,198,401 (Hlatky and Turner).
  • Olefin polymerization catalysts which contain a group 4 metal and one cyclopentadienyl ligand, one phosphinimine ligand and two monoanionic activatable ligands are disclosed in a commonly assigned patent application (Stephan et al).
  • the catalysts of Stephan et al axe group 4 metals in the 4 + oxidation state.
  • olefin polymerization catalysts which contain a group 4 metal, a cyclopentadienyl ligand or phosphinimine ligand and only one activatable ligand.
  • a preferred family of these catalysts contains Ti(lll) and offers an excellent kinetic profile when used in olefin polymerization.
  • the present invention provides a catalyst component for olefin polymerization which is an organometallic complex defined by the formula:
  • Cp is a cyclopentadienyl-type ligand
  • L is an activatable ligand
  • M is a metal selected from Ti and Zr
  • PI is a phosphinimine ligand defined by the formula:
  • each R 1 is independently selected from the group consisting of a hydrogen atom, a halogen atom, C1.2 0 hydrocarbyl radicals which are unsubstituted by or further substituted by a halogen atom, a C ⁇ - 8 alkoxy radical, an amido radical, a C ⁇ -io aryl or aryloxy radical, a silyl radical of the formula:
  • each R 2 is independently selected from the group consisting of hydrogen, a C ⁇ - 8 alkyl or alkoxy radical, C 6 - ⁇ o aryl or aryloxy radicals, and a germanyl radical of the formula:
  • the catalyst component of this invention is a group 4 metal selected from titanium and zirconium.
  • the catalyst component of this invention must contain a phosphinimine ligand which is covalently bonded to the metal. This ligand is defined by the formula:
  • R 1 ⁇ R 1 — P N - / R 1 wherein each R 1 is independently selected from the group consisting of a hydrogen atom, a halogen atom, C ⁇ -2 o hydrocarbyl radicals which are unsubstituted by or further substituted by a halogen atom, a C ⁇ - 8 alkoxy radical, a C 6- ⁇ o aryl or aryloxy radical, an amido radical, a silyl radical of the formula:
  • each R 2 is independently selected from the group consisting of hydrogen, a Ci-s alkyl or alkoxy radical, C 6 - ⁇ o aryl or aryloxy radicals, and a germanyl radical of the formula:
  • the preferred phosphinimines are those in which each R 1 is a hydrocarbyl radical.
  • a particularly preferred phosphinimine is tri-(tertiary butyl) phosphinimine (i.e. where each R 1 is a tertiary butyl group).
  • Cvclopentadienyl-Tvpe Ligand The term cyclopentadienyl-type ligand (or "Cp ligand”) refers to a ligand which is cyclic and forms a delocalized pi-bond with the group 4 transition metal.
  • Cp ligands includes substituted (or unsubstituted) cyclopentadienyl ligands, substituted (or unsubstituted) indenyl ligands, and substituted (or unsubstituted) fluorenyl ligands.
  • substituents on such cyclic ligands is well known and is described, for example, in USP 5,324,800 (Welborn).
  • An exemplary list of substituents for such Cp ligands includes C 1 - 20 hydrocarbyl groups; substituted C ⁇ -2 o hydrocarbyl groups wherein one or more hydrogen atoms is replaced by a halogen; an amido group, a phosphido group, or an alkoxy group.
  • the substituent may form a bridge with the phosphinimine ligand.
  • the Cp ligand is a cyclopentadienyl or indenyl ligand.
  • activatable ligand refers to a ligand which may be activated by a cocatalyst (also known as an "activator” to facilitate olefin polymerization.
  • exemplary activatable ligands are independently selected from the group consisting of a hydrogen atom, a halogen atom, a C M O hydrocarbyl radical, a CMO alkoxy radical, a C 5 - ⁇ 0 aryl oxide radical; each of which said hydrocarbyl, alkoxy, and aryl oxide radicals may be unsubstituted by or further substituted by a halogen atom, a C ⁇ -8 alkyl radical, a C ⁇ - 8 alkoxy radical, a C 6 - ⁇ o aryl or aryl oxy radical, an amido radical which is unsubstituted or substituted by up to two C ⁇ - 8 alkyl radicals; a phosphido radical which is unsubstituted or substituted by up to two
  • the catalyst components described in part 1 above are used in combination with an "activator” (which may also be referred to by a person skilled in the art as a “cocatalyst”) to form an active catalyst system for olefin polymerization.
  • an "activator” which may also be referred to by a person skilled in the art as a “cocatalyst”
  • Simple aluminum alkyls and alkoxides may provide comparatively weak cocatalytic activity under certain mild polymerization conditions.
  • the preferred activators are alumoxanes and so- called ionic activators, as described below. 2.1 Alumoxanes
  • the alumoxane activator may be of the formula: (R 4 ) 2 AIO(R 4 AIO) m AI(R 4 ) 2 wherein each R 4 is independently selected from the group consisting of C1-2 0 hydrocarbyl radicals and m is from 0 to 50, preferably R 4 is a C ⁇ - alkyl radical and m is from 5 to 30.
  • Methylalumoxane (or "MAO") is the preferred alumoxane.
  • Alumoxanes are well known as activators for metallocene-type catalysts.
  • Activation with alumoxane generally requires a molar ratio of aluminum in the activator to (group 4) metal in the catalyst from 20:1 to 1000:1. Preferred ratios are from 50:1 to 250:1. 2.2 Ionic Activators
  • Ionic activators are also well known for metallocene catalysts. See, for example, USP 5,198,401 (Hlatky and Turner). These compounds may be selected from the group consisting of:
  • each R 7 is independently selected from the group consisting of phenyl radicals which are unsubstituted or substituted with from 3 to 5 substituents selected from the group consisting of a fluorine atom, a Ci-4 alkyl or alkoxy radical which is unsubstituted or substituted by a fluorine atom; and a silyl radical of the formula -Si-(R 9 ) 3 ; wherein each R 9 is independently selected from the group consisting of a hydrogen atom and a C ⁇ - 4 alkyl radical; and
  • Ci -4 alkyl radical or R 8 taken together with the nitrogen atom forms an anilinium radical which is substituted by two C ⁇ -4 alkyl radicals.
  • the "ionic activator” may abstract the activatable ligand so as to ionize the catalyst center into a cation but not to covalently bond with the catalyst and to provide sufficient distance between the catalyst and the ionizing activator to permit a polymerizable olefin to enter the resulting active site.
  • ionic activators include: triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tripropylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(m,m-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tri(n-butyl)ammonium te
  • Readily commercially available ionic activators include: N,N- dimethylaniliumtetrakispentafluorophenyl borate; triphenylmethylium tetrakispentafluorophenyl borate; and trispentafluorophenyl borane. 3. Homogeneous or Heterogeneous Catalyst
  • the catalyst system of this invention may be used in a homogeneous form in solution polymerization (where the term “homogeneous” means that the catalyst and cocatalyst/activator are soluble in, or miscible with, the polymerization solvent).
  • homogeneous means that the catalyst and cocatalyst/activator are soluble in, or miscible with, the polymerization solvent.
  • the catalyst when employed in a slurry or gas phase polymerization, it is highly preferred to use the catalyst in a heterogeneous or "supported form”. It is also highly preferred that the catalyst does not cause reactor fouling.
  • heterogeneous catalysts may be grouped into three main categories:
  • Friable catalyst particles lead to the formation of "fines" in the polyethylene product, and may also aggravate reactor fouling problems.
  • An alternative approach is the preparation of spray dried catalysts using a hydrotalcite as a "reactive" filler (as opposed to the unreactive filler described in the above-mentioned USP to Union Carbide). This method of catalyst preparation is described in more detail in a commonly assigned patent application. Either approach is suitable for use with the catalysts of this invention. 4. Polymerization Processes
  • the catalysts of this invention are suitable for use in any conventional olefin polymerization process, such as the so-called "gas phase”, “slurry”, “high pressure” or “solution” polymerization processes.
  • the polymerization process according to this invention uses ethylene and may include other monomers which are copolymerizable therewith such as other alpha olefins (having from three to ten carbon atoms, preferably butene, hexene or octene) and, under certain conditions, dienes such as hexadiene isomers, vinyl aromatic monomers such as styrene or cyclic olefin monomers such as norbornene.
  • alpha olefins having from three to ten carbon atoms, preferably butene, hexene or octene
  • dienes such as hexadiene isomers
  • vinyl aromatic monomers such as styrene or cyclic olefin monomers such as norbornene.
  • the present invention may also be used to prepare elastomeric co- and terpolymers of ethylene, propylene and optionally one or more diene monomers.
  • elastomeric polymers will contain about 50 to abut 75 weight % ethylene, preferably about 50 to 60 weight % ethylene and correspondingly from 50 to 25% of propylene.
  • a portion of the monomers, typically the propylene monomer, may be replaced by a conjugated diolefin.
  • the diolefin may be present in amounts up to 10 weight % of the polymer although typically is present in amounts from about 3 to 5 weight %.
  • the resulting polymer may have a composition comprising from 40 to 75 weight % of ethylene, from 50 to 15 weight % of propylene and up to 10 weight % of a diene monomer to provide 100 weight % of the polymer.
  • the dienes are dicyclopentadiene, 1 ,4-hexadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene.
  • Particularly preferred dienes are 5-ethylidene-2-norbomene and 1 ,4-hexadiene.
  • the polyethylene polymers which may be prepared in accordance with the present invention typically comprise not less than 60, preferably not less than 70 weight % of ethylene and the balance one or more C 4- ⁇ 0 alpha olefins, preferably selected from the group consisting of 1-butene, 1-hexene and 1-octene.
  • the polyethylene prepared in accordance with the present invention may be linear low density polyethylene having density from about 0.910 to 0.935 g/cc.
  • the present invention might also be useful to prepare polyethylene having a density below 0.910 g/cc - the so-called very low and ultra low density polyethylenes.
  • the most preferred polymerization process of this invention encompasses the use of the novel catalysts (together with a cocatalyst) in a medium pressure solution process.
  • the term "medium pressure solution process” refers to a polymerization carried out in a solvent for the polymer at an operating temperature from 100 to 320°C (especially from 120 to 220°C) and a total pressure of from 3 to 35 mega Pascals. Hydrogen may be used in this process to control (reduce) molecular weight.
  • Optimal catalyst and cocatalyst concentrations are affected by such variables as temperature and monomer concentration but may be quickly optimized by non-inventive tests.
  • the catalyst of this invention may also be used in a slurry polymerization process or a gas phase polymerization process.
  • the typical slurry polymerization process uses total reactor pressures of up to about 50 bars and reactor temperature of up to about 200°C.
  • the process employs a liquid medium (e.g. an aromatic such as toluene or an alkane such as hexane, propane or isobutane) in which the polymerization takes place. This results in a suspension of solid polymer particles in the medium.
  • Loop reactors are widely used in slurry processes. Detailed descriptions of slurry polymerization processes are widely reported in the open and patent literature.
  • a fluidized bed gas phase polymerization reactor employs a "bed" of polymer and catalyst which is fluidized by a flow of monomer which is at least partially gaseous.
  • Heat is generated by the enthalpy of polymerization of the monomer flowing through the bed. Unreacted monomer exits the fluidized bed and is contacted with a cooling system to remove this heat. The cooled monomer is then re-circulated through the polymerization zone together with "make-up" monomer to replace that which was polymerized on the previous pass.
  • the "fluidized” nature of the polymerization bed helps to evenly distribute/mix the heat of reaction and thereby minimize the formation of localized temperature gradients (or "hot spots"). Nonetheless, it is essential that the heat of reaction be properly removed so as to avoid softening or melting of the polymer (and the resultant-and highly undesirable - “reactor chunks").
  • the obvious way to maintain good mixing and cooling is to have a very high monomer flow through the bed. However, extremely high monomer flow causes undesirable polymer entrainment.
  • An alternative (and preferable) approach to high monomer flow is the use of an inert condensable fluid which will boil in the fluidized bed (when exposed to the enthalpy of polymerization), then exit the fluidized bed as a gas, then come into contact with a cooling element which condenses the inert fluid. The condensed, cooled fluid is then returned to the polymerization zone and the boiling/condensing cycle is repeated.
  • condensed mode operation and is described in additional detail in USP 4,543,399 and USP 5,352,749. As noted in the '399 reference, it is permissible to use alkanes such as butane, pentanes or hexanes as the condensable fluid and the amount of such condensed fluid preferably does not exceed about 20 weight per cent of the gas phase.
  • Preferred Polymerization Temperatures about 75°C to about 115°C (with the lower temperatures being preferred for lower melting copolymers - especially those having densities of less than 0.915 g/cc - and the higher temperatures being preferred for higher density copolymers and homopolymers); and
  • Pressure up to about 1000 psi (with a preferred range of from about 100 to 350 psi for olefin polymerization).
  • Part A Catalyst Component Synthesis
  • Part B Solution Polymerization
  • Part C Gel Phase Polymerization
  • GPC Gel permeation chromatography
  • Polymer densities were measured using pressed plaques (ASTM method D-1928-90), with a densitometer.
  • Ph phenyl
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • PE polyethylene
  • Electron Paramagnetic Resonance (ESR) g 1.9752. This g value confirms the presence of the Ti(lll) species.
  • ESR Electron Paramagnetic Resonance
  • the polymerization time was 10 minutes in each experiment.
  • the reaction was terminated by adding 5 mL of methanol to the reactor and the polymer was recovered by evaporation of the cyclohexane.
  • the polymerization activities were calculated based on the ethylene consumed during the reaction, not the weight of the polymer produced.
  • Polymer molecular weights and molecular weight distributions were measured by GPC (Waters 150-C) at 140°C in 1 ,2,4-trichlorobenzene calibrated using polyethylene standards.
  • the polyethylene produced by the inventive catalyst RS-676-89 has a low molecular weight tail, which contributes to a higher polydispersity of 5.4.
  • the inventive experiment using RS-676-89 showed a different kinetic profile which may be a result of the Ti(lll) species.
  • the "initial" activity of the inventive experiment was slower/lower, but the overall activity was high. This is very desirable for commercial-scale polymerizations having a residence time of more than 2 minutes. PART B2 The Continuous Solution Polymerization
  • the catalyst solutions were pumped to the reactor independently and in some cases were mixed before entering the polymerization reactor (as indicated in the examples). Because of the low solubility of the catalysts, activators and MAO in cyclohexane, solutions were prepared in purified xylene.
  • the catalyst was activated in-situ (in the polymerization reactor) at the reaction temperature in the presence of the monomers.
  • the polymerizations were carried out in cyclohexane at a pressure of 1500 psi.
  • Ethylene was supplied to the reactor by a calibrated thermal mass flow meter and was dissolved in the reaction solvent prior to the polymerization reactor. If comonomer (for example 1-octene) was used it was also premixed with the ethylene before entering the polymerization reactor. Under these conditions the ethylene conversion is a dependent variable controlled by the catalyst concentration, reaction temperature and catalyst activity, etc.
  • the internal reactor temperature is monitored by a thermocouple in the polymerization medium and can be controlled at the required set point to +/- 0.5°C. Downstream of the reactor the pressure was reduced from the reaction pressure (1500 psi) to atmospheric. The solid polymer was then recovered as a slurry in the condensed solvent and was dried by evaporation before analysis.
  • the ethylene conversion was determined by a dedicated on line gas chromatograph by reference to propane which was used as an internal standard.
  • the average polymerization rate constant was calculated based on the reactor hold-up time, the catalyst concentration in the reactor and the ethylene conversion and is expressed in l/(mmo min).
  • Average polymerization rate (kp) (0/(100-Q)) x (1/[TM]) x (1/HUT) ' where : Q is the percent ethylene conversion.
  • [TM] is the catalyst concentration in the reactor expressed in mM.
  • HUT is the reactor hold-up time in minutes.
  • Melt index (Ml) measurements were conducted according to ASTM method D-1238-82.
  • CpTiNP( t Bu) 3 (butadiene) and Ph 3 C B(CeF 5 ) 4 were mixed before the reactor and were subsequently mixed with the MMAO-7 in the reactor.
  • the reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor as was 3.0 ml/min of 1-octene. An ethylene conversion of 91.3% was observed (see Table B2.1).
  • CpTiNP( , Bu) 3 (butadiene) and Ph 3 C B(C 6 F 5 ) 4 were mixed before the reactor and were subsequently mixed with the MMAO-7 in the reactor.
  • the reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor as was 5.0 ml/min of 1-octene. An ethylene conversion of 90.5% was observed (see Table B2.1).
  • CpTiNP( l Bu) 3 (butadiene) and Ph 3 C B(C 6 F 5 ) 4 were mixed before the reactor and were subsequently mixed with the MMAO-7 in the reactor.
  • the reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor as was 1.0 ml/min of 1 -octene. An ethylene conversion of 91.3% was observed (see Table B2.1).
  • CpTiNP( l Bu) 3 (butadiene) and Ph 3 C B(C 6 F 5 ) 4 were mixed before the reactor and were subsequently mixed with the MMAO-7 in the reactor.
  • the reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor. An ethylene conversion of 90.7% was observed (see Table B2.1).
  • the reaction temperature was 160°C and 2.1 gram/min of ethylene was continuously added to the reactor. An ethylene conversion of 94.6% was observed (see Table B2.1).
  • the reaction temperature was 160°C and 2.1 gram/min of ethylene and 3.25 ml/min of 1-octene was continuously added to the reactor. An ethylene conversion of 94.8% was observed (see Table B2.1).
  • the supported catalysts were prepared by initially supporting MAO on a silica support, followed by deposition of the catalyst component.
  • the catalyst was activated in-situ (in the polymerization reactor) at the reaction temperature in the presence of the monomers, using a metal alkyl complex which has been previously added to the reactor to remove adventitious impurities. Purified and rigorously anhydrous sodium chloride was used as a catalyst dispersing agent.
  • the internal reactor temperature is monitored by a thermocouple in the polymerization medium and can be controlled at the required set point to +/- 1.0°C.
  • the duration of the polymerization experiment was one hour.
  • the polymer was separated from the sodium chloride and the yield determined.
  • Table C1 illustrates data concerning the Al/transition metal ratios of the supported catalyst and polymer yield. Polymer properties are shown in Table C2.
  • inventive complexes are well suited for use as a component in a catalyst system for the polymerization of olefins, especially ethylene.
  • Polyethylene produced with the inventive complexes is useful, for example, in the production of film, extruded parts and profiles and molded plastic goods.

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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne des complexes organométalliques de titane ou zirconium ayant seulement trois ligands (notamment un ligand cyclopentadiényle, un ligand phosphinime et un ligand activable) et constituant des composants catalytiques pour la polymérisation oléfinique. On prépare de préférence des systèmes de polymérisation en combinant les complexes organométalliques avec un activateur ionique et/ou un alumoxane. Les composants catalytiques renferment de préférence du titane (III) et sont utilisés dans la polymérisation d'éthylène.
PCT/CA1999/000526 1998-07-21 1999-06-08 Catalyseur au cyclopentadienyl/phosphinime avec un et un seul ligand activable WO2000005236A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BRPI9912316-9A BR9912316B1 (pt) 1998-07-21 1999-06-08 catalisador de ciclopentadienil/fosfinimina com um e somente um ligando ativável.
AT99924614T ATE228141T1 (de) 1998-07-21 1999-06-08 Cyclopentadienyl / phosphinimine katalysator mit einem und nur einem aktivierbaren ligand
DE69904061T DE69904061T2 (de) 1998-07-21 1999-06-08 Cyclopentadienyl / phosphinimine katalysator mit einem und nur einem aktivierbaren ligand
EP99924614A EP1112276B1 (fr) 1998-07-21 1999-06-08 Catalyseur au cyclopentadienyl/phosphinime avec un et un seul ligand activable
AU41263/99A AU4126399A (en) 1998-07-21 1999-06-08 Cyclopentadienyl /phosphinimine catalyst with one and only one activatable ligand
JP2000561192A JP4377061B2 (ja) 1998-07-21 1999-06-08 唯一つだけの活性化可能な配位子を有するシクロペンタジエニル／ホスフィンイミン触媒

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CA002243726A CA2243726C (fr) 1998-07-21 1998-07-21 Catalyseur au cyclopentadienyle/phosphinimine a un seul ligand d'activation
CA2,243,726 1998-07-21

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WO2000005236A1 true WO2000005236A1 (fr) 2000-02-03

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US (1) US6355744B1 (fr)
EP (1) EP1112276B1 (fr)
JP (1) JP4377061B2 (fr)
KR (1) KR100533925B1 (fr)
CN (1) CN1161364C (fr)
AT (1) ATE228141T1 (fr)
AU (1) AU4126399A (fr)
BR (1) BR9912316B1 (fr)
CA (1) CA2243726C (fr)
DE (1) DE69904061T2 (fr)
ES (1) ES2187161T3 (fr)
WO (1) WO2000005236A1 (fr)

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WO2008148499A1 (fr) * 2007-06-06 2008-12-11 Dsm Ip Assets B.V. Catalyseur à base d'imine
WO2008151776A1 (fr) * 2007-06-12 2008-12-18 Dsm Ip Assets B.V. Catalyseur de type imine
US8901334B2 (en) 2012-12-21 2014-12-02 Governors Of The University Of Alberta Transition metal-phosphoranimide catalysts
US9000198B2 (en) 2013-05-21 2015-04-07 Governors Of The University Of Alberta Mixed-valent transition metal-phosphoranimide catalysts
US9051229B2 (en) 2012-12-21 2015-06-09 Governors Of The University Of Alberta Transition metal catalysts for C—O hydrogenolysis and hydrodeoxygenation
US9120984B2 (en) 2012-12-21 2015-09-01 Governors Of The University Of Alberta Transition metal catalysts for hydrodesulfurization
US9120741B2 (en) 2012-12-21 2015-09-01 Governors Of The University Of Alberta Transition metal catalysts for hydrogenation and hydrosilylation
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Publication number Priority date Publication date Assignee Title
EP1162214A1 (fr) * 2000-06-08 2001-12-12 Nova Chemicals (International) S.A. Procédé de préparation d'élastomère éthylène-propylène
JP2002020416A (ja) * 2000-06-08 2002-01-23 Nova Chem Internatl Sa エチレンプロピレンエラストマーの調製方法
WO2008148499A1 (fr) * 2007-06-06 2008-12-11 Dsm Ip Assets B.V. Catalyseur à base d'imine
WO2008151776A1 (fr) * 2007-06-12 2008-12-18 Dsm Ip Assets B.V. Catalyseur de type imine
US8901334B2 (en) 2012-12-21 2014-12-02 Governors Of The University Of Alberta Transition metal-phosphoranimide catalysts
US9051229B2 (en) 2012-12-21 2015-06-09 Governors Of The University Of Alberta Transition metal catalysts for C—O hydrogenolysis and hydrodeoxygenation
US9120984B2 (en) 2012-12-21 2015-09-01 Governors Of The University Of Alberta Transition metal catalysts for hydrodesulfurization
US9120741B2 (en) 2012-12-21 2015-09-01 Governors Of The University Of Alberta Transition metal catalysts for hydrogenation and hydrosilylation
US9000198B2 (en) 2013-05-21 2015-04-07 Governors Of The University Of Alberta Mixed-valent transition metal-phosphoranimide catalysts
US9458395B2 (en) 2013-05-21 2016-10-04 Governors Of The University Of Alberta Catalysts for hydrodesulfurization

Also Published As

Publication number Publication date
AU4126399A (en) 2000-02-14
BR9912316B1 (pt) 2010-06-01
BR9912316A (pt) 2001-05-08
KR20010070992A (ko) 2001-07-28
JP4377061B2 (ja) 2009-12-02
ATE228141T1 (de) 2002-12-15
CA2243726A1 (fr) 2000-01-21
CN1161364C (zh) 2004-08-11
DE69904061T2 (de) 2003-07-17
EP1112276A1 (fr) 2001-07-04
KR100533925B1 (ko) 2005-12-07
EP1112276B1 (fr) 2002-11-20
DE69904061D1 (de) 2003-01-02
JP2002521500A (ja) 2002-07-16
CN1319103A (zh) 2001-10-24
CA2243726C (fr) 2006-12-12
US6355744B1 (en) 2002-03-12
ES2187161T3 (es) 2003-05-16

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